CA2061874A1 - Polymers modified by ketonic and ether-ketonic compounds - Google Patents

Abstract

TITLE
POLYMERS MODIFIED BY KETONIC AND ETHER-KETONIC COMPOUNDS
ABSTRACT OF DISCLOSURE
Polymers comprising carbonyl groups in their backbone, such as polyesters and polyimides, which have been modified by compounds having ketonic groups in their backbone, and molecular weights in the region of 300 to under 1,000. Preferably, these compounds have also ether groups in their backbone.

Description

2~6~74 TITLE
POLYMERS MODIFIED BY XETONIC AND ETHER-KETONIC COMPOUNDS
FIELD OF ~HE INVENTION
This inventlon relates to polymers comprising carbonyl groups $n thelr backbone, such as polyesters and polyimides, which have been modified by compounds having ketonic groups in their backbone. Preferably, these compounds have also ether groups in their backbone.
BACKGROUND OF THE INVENTION
A number of polymers which contain carbonyl groups in their backbones, such as for example polyesters and polyimides, depending on their structure, may be hard, stiff, and difficult to process. ~owever, they are valuable because of other desirable properties, which vary depending on the applicatlon.
Polyesters are usually less expensive than polyimides, and they may be preferred to polylmides for thls reason ln a number of occaslons, lf the requlrements for the partlcular appllcation permit; for example, lf the end-use temperature 18 not very high.
Polylmldes constitute a class of valuable polymers belng characterlzed by thermal stablllty, lnert character, usual lnsolublllty in even strong solvents, and high Tg, among others. Their precursors are usually polyamic aclds, which may take the final lmidized form either by thermal or by chemical treatment. Polyimldes have always found a large number of appllcatlons requlrlng the aforementioned characterlstics ln numerous lndustrles, and recently thelr appllcatlons have started lncreaslng dramatically ln electronlc devlces, especially as dielectrics. Wlth continuously escalating sophlstlcatlon ln such devlces, the demands on the 2 2 ~ 7 ~

propertles and the property control are becoming rather vexatious. Especially for the electronics industry, improvements of polyimides are needed in forming tough, pin-hole free coatings, having lower dielectric constant, lower coeff$cient of thermal expansion, lower moisture absorption, and decreased stiffness, among others. Although it is not usually possible to maximize all properties, slnce many of them may be antagonistic, optimization as a total is highly desirable and it may be achieved if adequate control on the properties becomes available through molecular architecture or other means.
One of the ma~or problems is that in many instances, when all other properties have been optimized, stiffness and difficult processibility, such as thermal processing, remain unresolved, due mainly to very high Tg, and very high viscosity above Tg.
In order to overcome thls difficulty, polyethers and polyetherketones of at least moderate average molecular weight have been utilized in the past, admixed with the polyesters and the polyimides under conslderation for lowering the Tg. Commonly used plasticizers with other polymers are avoided in this case as sub~ect to exudation sooner or later, and other disadvantages, such as for example lack of high thermal stability, volatility at high processing temperatures, and the like.
Misclble blends of polytaryl ether ketone~s and polyetherimide9 are described by Harris et al. ln the Journal of Applled Polymer Science, Vol. 35, pp. 1877-1891 (1988).
U.S. Patent 4,532,305 ~Dicklnson), lssued 7/30/85, descrlbes a plastlclzed thermoplastic polymer compositlon comprlsing ln admlxture, a thermoplastic 3 2~6~7~

polymer selected from a polyarylate, a polyetherimide, an aromatic polycarbonate, a poly~aryl ether) having a molecular weight in excess of 10,000 and mixtures thereof and a plastlcizing amount of a poly(aryl ether) having a molecular weight of from about 1,000 to about 5,000.
U.S. Patent 4,250,279 (Robeson et al), issued 2/10/81, describes molding compositions of blends of a polyarylate deri~ed from a dihydric phenol and an aromatic dicarboxylic acid, and a polyetherimide. These blends can additionally contain thermoplastic polymers which are compatible with the blend of polyarylate and polyetherimide.
U.S. Patent 4,293,670 (Robeson et al), issued 10/6/81, describes moldlng compositions of blends of a poly~aryl ether) resin and a polyetherimide resin.
These compositions are claimed to have improved environmental stress crack resistance.
U.S. Patent 4,613,645 (Robeson et al), issued 9/23/86, descrlbes thermoplastic, ln~ection moldable composltes comprising at least one poly~aryl ether ketone) havlng silicon carbide whiskers dispersed thereln exhlblt excellent tenslle properties coupled wlth high elongation relative to poly(aryl ether ketone) composltes with other inorganic fibers. The composltes are useful for making artlcles such as electrical connectors.
U.S. Patent 4,703,081 ~Blackwell et al.), issued 10/27/87, descrlbe~ a ternary polymer alloy containing a poly~arylene sulflde), a poly(amide lmide), and at least one of a poly~aryl ketone) and a poly~aryl sulfone).
The polymer alloy optionally can contaln a flbrous relnforclng materlal such as a glass flber.

4 20~74 U.S. Patent 4,704,448 (Brugel), lssued 11/3/87, descrlbes copolyetherketones derived from dlphenyl ether and aromatic diacids or diacid halides where the diphenyl ether is present ln a molar excess relative to the diacid or diacid halide chlorides of about 2 to 8%.
U.S. Patent 4,720,537 (Brugel), issued 1/19/88, descrlbes branched copolyetherketones comprising condensation products of diphenyl ether, aromatic acid halides and trifunctlonal comonomers.U.S. Patent 4,816,556 ~Gay et al.), ls~ued 3/2B/89, descr~bes ordered copolymers of tere- and isophthalyl halides with diphenyl ether where the phthalyl groups alternate or where the terephthalyl or lsophthalyl groups are in blocks. These ordered copolyetherketones exhibit a lS higher level of crystallization and more rapid crystallinity behavior than corresponding random copolyetherketones. They also form completely miscible blends wlth certaln aromatic polyetherimides.
European Patent Application Publicatlon 0 167 897 Al ~Dicklnson), publlshed Jan. 15, 1986, is directed to a plastlclzed polyarylate composltlon comprlslng in admlxture, a polyarylate, derlved rom a dlhydrlc phenol and at least one aromatlc dlcarboxylic acld and havlng a reduced vlscoslty o from about 0.4 to greater than l.dc/g, rom about S to 30 welght per cent of glass flbers, and a plastlclzlng amount of an ollgomerlc poly(aryl) ether havlng a reduced vlscoslty of from about 0.1 to about 0.45 dl/g.
Some o the ma~or problems wlth the approaches suggested thus far are that polyethers and polyetherketones:

2~6~87~

have a more or less broad distribution of molecular weights as being polymers or oligomers, which prevents good reproduc~b~llty, their efflclency is low and are needed ln relatively large amounts to exhibit an appreciable effect, and they may lntroduce undesirable phenomena, due to the high concentration required.

In contrast, the present invention utilizes ketone and etherketone compounds as opposed to polymers or oligomers, which have molecular weights in a specific range between about 300 and under 1,000. Compounds are substantially monodisperse moietles, while polymers or ollgomers have typically a large polydispersity, unless speciflc procedures have been used ln their preparation.
Even then, only in limited sltuations lt ls possible to reach a polydisperslty lower than 2. In addition, the compatlbility of lower molecular welght species, especlally ln the case of some polyesters, particularly ls better with lower molecular welght moletles. These differences are very lmportant to the present invention, as lt will be seen herelnunder.
None of the above references descrlbes, suggests, or implies compositions, where the modlfler is a ketonic compound, preferably contalnlng ether groups ln the backbone, and havlng a molecular welght in the region of 300 to under 1,000. In addltion, none of the references recognizss the lmportance of utllizlng ln the composltlon substantlall~ monodisperse modifiers.

6 2061~74 summary of the Tnvention ~ he instant invention is dlrected to polymers comprising carbonyl groups in their backbone, such as polyesters and polyimides, which have been modified by S compounds havinq ketonlc groups in their backbone, and molecular weights ln the region of 300 to under 1,000.
Preferably, these compounds have also ether groups in their backbone. More particularly, this inventlon pertains to a composit$on of matter comprising:
(a) a condensation polymer selected from the group consisting of polyester and polyimide, and ~ b) a modifier consisting essentially of a compound having a formula R2-Rl-RO_Rl_R2 wherein R0 is O O
--C-- or --C~ c_ o Rl is ~ O -R2 iS
o --H or --C~

7 2 ~ 7 ~

This invention also pertains to a compositlon of matter comprising:
(a) a condensation polymer selected from the ~roup consisting of polyester and polyimide, and ~b) a modlfier consisting essentially of a compound having a formula O O
~C~O~C~

or ~C~C~

Preferably, the modifier in both cases has a polydispersity of substantially 1.

~etailed ne~cript~On of the Tnvention The instant lnvention ls directed to polymers comprisin~ carbonyl groups ln their backbone, such as polyesters and polyimldes, which have been modified by compounds, as opposed to polymers, havlng ketonic groups in their backbone, and molecular weights in the region of 300 to under 1,000. Preferably, these compounds have also ether groups in their backbone.
~he polyesters and polyimides utillzed ln the practice of tbe present invention, preferably aromatic for better thermal stabillty, may be prepared in any number of conventlonal ways well known to the art.
Depending on their structure and on the functlon that they have to fulfill, however, they may be too hard, or too ~tiff, or too difflcult to process thermally, and the like. Nevertheless, many times they are valuable 8 20~187~

because of other des$rable properties, which vary, depending on the final application.
In the past, as aforementioned, in order to overcome this diff$culty, polyethers and polyetherketones of at least moderate weight average molecular weight in the form of oligomers or polymers have been utilized, admixed with the polyesters and the polylmides under consideration for lowering the T~.
Some of the advantages of using compounds instead of polymers as modifiers in the compositions of the present invention are:

since compounds have a narrow distribution of molecular weights when compared to polymers, the reproduclbility achieved ln their use is very high; and their efficiency is high, and thus they are needed ln relatlvely small amounts ln order to exhibit an appreciable effect;

Slnce the compounds of the present lnvention have molecular welghts in the range of 300-1000, they are adequately non-volatlle to substantially avold evaporatlon durlng curing or processing of the polymer whlch they modlfy, and at the same time thelr effect, especially regardlng Tg and melt vlscosity, ls maxlmized.
The level of modlfler that can be lncorporated into a polylmlde or polyester may be determlned partially by the mlsclblllty characterlstlcs of the compound wlth the structure of the polymer. For polyester materlals, lt ls expected that many structures are mlsclble with the modlflers, whlle others, especlally those of the llquld 9 2 ~ 7 ~

crystal polymer (LCP~ variety, may be immiscible or display a miscibility limit based on structure. In that case, a point is reached where the compound no longer forms a homogeneous blend and phase-separates from the S polymer. Such a situation is normally undeslrable from a property standpoint, so that exceedlng this llmit should typically be avoided. Llkewise, many dlfferent polyimide and polyetherimide structures are also expected to be miscible with the modifying compounds;
~0 however, some structures, especially those of very rigid nature, e.g., BPDA/PPD or PMDA/PPD) may be expected to have a lower miscibility limit or be immiscible. The level at which a miscibility llmlt occurs is governed to some extent by the molecular weight of the modifier.
Generally, the hlgher the molecular weight, the lower the miscibility limit in the polymer. On the other hand, whlle a lower molecular weight additive tends to have a larger impact on properties and better misclbility, a lower limit of molecular weight is reached, beyond which the volatillty of the modlfler ls undeslrably high at polymer processlng temperatures.
The level of modifier that can be lncorporated may also be llmited by the amount that can be used while malntalning desired mechanical property levels, since low molecular weight compounds would be typlcally be expected to deterlorate the mechanlcal propertles of polymers when used ln excesslve amounts.
Often, polyimides may be prepared which exhibit crystalllne transitlon~s) as-prepared, but lose this crystalllnity once heated or processed about the transltlon temperature. Normally, thls crystalllnlty ls not recoverable. Slnce lt ls known that crystalllnlty ln polymer often leads to useful property lmprovements, e.g.,. strength, modulus, solvent reslstance, lt ls lo 2~6187~

desirable to develop methods whereby crystallinity in polyimides may be achieved or enhanced. Such methods in which the solvent N-methyl-2-pyrrolidone is used to treat amorphous samples of a poly~mide known commonly as S LARC-TPI are known to the artisans. Although this method has been shown to lnduce crystallinity in LARC-TPI, generally ~olvent treatment after processing to lnduce crystallinity ln prepared parts ls undesirable from a commercial standpolnt. It would be preferred to have a crystallinlty promoter or enhancer as part of the polymer mixture that could function during polymer processing. The compounds of the present lnventlon fulfill such a need ln that lt has been demonstrated that crystallinity may be achieved during melt processing of a polyimide such that a semicrystalline polyimide may be achieved directly from extrusion or in~ection molding. The compounds of the present inventlon have the advantage over solvents ln that their hlgher molecular welght and low volatlllty minlmizes their 1085 vla outgassing during high temperature processing and the shrinkage and volding that might accompany such 10s8.
Table 1 summarizes the performance of modifier in polylmides. It 18 very important to note that even small amounts, ln the reglon of 5-10% by weight, decrease tne water absorptlon conslderably. Also in the Examples, lt 18 shown that the melt viscoslty and Tg decrease appreclably with relatively small amounts of modlfler. The crystalllzatlon of polyimides may also be enabled or enhanced by the presence of the modifying compound5 of the present lnventlon. Often, the more crystalllne a polymer the better its functional properties, such a8 for example solvent resistance, heat 11 2061~74 resistance, and the like. This ls a very high attribute that the modifiers of the present invention offer.
It is worth noting, that depending on the appllcatlon, a soluble modifler may be required, such as in the case where, the polyimide for example is to be applled on a substrate as a coatlng from solvent at room temperature. Indeed, one may use ln such an occasion 1,3-bis(4-phenoxybenzoyl)benzene ~DID), whlch is soluble ln N-methyl-2-pyrrolidone at room temperature. On the other hand, 1,4-bis(4-phenoxybenzoyl)benzene (DTD) is largely insoluble ln N-methyl-2-pyrrolidone at room temperature (it is only soluble at elevated temperatures) and lt may be used in other applications, such as for example for lowerlng the melt viscosity of otherwlse intractable polymers according to the present invention. However, polymers of the polyether ketone type are typically either lnsoluble, or have reduced solubility, or may increase solution viscosity in solution coatings, such that they are typically unsultable for additlon to poly~amic acid) solutions.
This is one of the reasons why polyether ketones or ollgomeric ether ketones are not as good as compounds of this lnventlon.
The composltions of the present lnvention comprise a condensation polymer selected from the group consistlng of polyesters and polylmides, having a weight average molecular welght higher than 10,000. It ls lmportant that the welght average molecular welght ls preferably hlgher than 15,000, more preferably higher than 20,000, and even more preferably ln the range of 30,000 to 300,000, 80 that lt provldes the polymer wlth generally good functional propertles.

12 2~61 ~7~

It is lmportant that a modifier is lncorporated in the polyimide or polyester by addition of a compound having a formula R2-Rl-RO_Rl_R2 where, RO is O O
--C-- or --C~ c _ o Rl is ~ ~ ~ or ~

R2 is o --H or --C~
The modifier compounds utilized according to the present invention may be made 50 that they have a polydispersity of substantlally 1, ln contrast to polymexic species containlng a larger number of the same 25 or similar units, which develop polydispersities differing considerably from 1.
In order.to obtain a substantlally monodisperse compound, lt may be necessary to use an excess of one of the reactants as for example in Examples 23 and 24. In these cases, for the synthesi~ of 1,3-bis ~4-13 2 ~ 7 4 phenoxybenzoyl)benzene or 1,4-bis(4-phenoxybenzoyl)benzene, an excess of diphenyl ether versus isophthaloyl chlorlde or terephthaloyl chlor~de o~ at least 3 to 1 or higher is preferable in order to prevent substantial amounts of ollgomeric poly ether ketones from forming which would detract from the utllity of thls invention. The amount of excess used is preferably the mlnlmum amount which under the chosen reaction conditions gives essentially monodisperse products. Levels higher than this further assure the monodispersity of the compound ~ut are less desirable because they increase the level of unreacted starting material whlch must be removed from the final product.
It has been found that excesses of at least 3 to 1 up to about 5 to 1 are most preferable in the synthesis of compounds of this type.
Composit~ons made by adding modifiers similar to those of the present lnventlon ln the form of low molecular weight tall of a polymeric species havlng high polydlsperslty are certalnly lnferlor when compared to composltlons made by addlng the modlfier of thls invention ln lts substantlally monodlsperse form. This ls because ln the former case the ma~or actlve ingredlent constltutes only a small amount of the total addltive, while ln the latter case lt constitutes substantlally 100% of the ma~or actlve ingredient. In the former case, it 18 not only that the active ingredlent 1~ added ln a grossly dlluted form, but also ln most instances, the lnactlve lngredlent ls undeslrable a8 an lngredlent of the polylmlde or polye~ter a8 lt may deterlorate thelr propextles, lncludlng reproduclblllty and solublllty.

14 2~ 4 It ls preferable that Rl is ~
and R2 i9 whlle R0 i~ preferably O O
--C or --C~C--O

In another preferable embodiment, Rl i8 ~~

and R2 i9 101 ~

whlle R0 i8 preferably o --C~~!`C
O

2~61~74 In still another preferred embodiment of this invention, the modifier is ~C~O~C~

or ~C~C~

Examples demonstrating the instant invention are given below for illustration purposes only, and should not be construed as restrictlng the scope or limits of this lnvention in any way. All parts and percents are by weight and degrees are in centigrade unless otherwise indicated.

~E8 1/s: Reciprocal seconds Avlmid K: Polyimide based on pyromellltic dianhydride from Du Pont, Wilmington, Delaware BDTDB: 1,4-bis{4-([4-benzoyllphenoxy)benzoyl~benzene BPDA: 3,3',4,4'-blphenyltetracarboxylic acid dianhydride CTE: Coefflcient of Thermal Expansion dHm: Heat of melting DID: 1,3-bis(4-phenoxybenzoyl)benzene 16 2~ 74 DSC: Dlfferentlal Scanning Calorimetry DTD: 1,4-bis(4-phenoxybenzoyl)benzene GPC: Gel Permeation Chromatography J/g: Joules per gram LCP: Liquid Crystal Polymer L/d: Length to diameter ratio ODBP: Oxydibenzophenone ODA: 4,4'-oxydianiline Pa.s: Pascal.seconds PMDA: Pyromellitic dlanhydride PPD: p-phenylenedlamine Pyralin~ PI-2540: PMDA/ODA poly~amic acid) solution from Du Pont, Wilmington, Delaware Pyralin~ PI-2611: BPDA/PPD poly~amic acid) solution from Du Pont, Wilmington, Delaware ~g: Glass transition temperature Tm: Melting temperature 2~61874 ~a~
In a glass container, 66.5 g of Avlmid K polyimide powder was dry blended with 3.5 g of 1,4-bis(4-phenoxybenzoyl)benzene (DTD) (9596 Avimid K, 5% DTD).

5 After drying overnight at approximately 125C to remove any moisture present, the mlxture was charged to a Haake torque rheometer (small bowl mixer, h$gh shear cam mlxing blades) at 360C, and mixed for 10 min at 64 rpm.
Afterwards, the polymer melt was removed from the mixer 10 vla a brass spatula, allowed to cool to room temperature and then ground to a coarse powder in a Thomas cutter.
DSC measurements (Du Pont 1090, 20C/min, 2nd heating scan) revealed a Tg of 236C and capillary melt rheology ~370C, L-.993, d - 0.029, L/d - 34.241) gave a melt viscosity of 1299 Pa.s at 385 l/s.

Comparative ExatVle 1 A slmilar procedure as that given in Example 1 was followed for Avimid K polylmide containing no l,4-bis(4-20 phenoxybenzoyl)benzene ~DTD). A very viscous meltresulted whlch caused a very high torque on the Haake lnstrument. DSC measurements showed a Tg of 260C for thls materlal and melt rheology yielded a melt viscosity of 2670 Pa.s at 385 l/s. The as-recelved Avimid K ~no 25 melt processing) exhlbited no readily discernable Tg and had a Tm of 351C, dHm - 26.9 J/g.

E~le 2 A simllar procedure as that given in Example 1 was 30 followed except that 63 g of Avimld X polyimide powder was blended wlth 7 g of 1,4-bis~4-phenoxybenzoyl)benzene (DTD) ~90~ Avlmid K, lO9~i DTD). The blend exhibited a Tg of 216C and a melt vlscoslty of 670 Pa.s at 385 l/s.

18 2~6187~

~x~ple 3 A similar procedure as that qiven ln Example 1 was followed except that 48 g of Avimid K polyimide powder was blended wlth B.S g of 1,4-bis(4-p~enoxybenzoyl)benzene ~DTD) ~85% Avimid K, 15 % DTD).The blend exh~bited a Tg of 194C. This blend als~
exhibited a bimodal Tm with endothermic maxima at 288 and 332~C, total dHm e 10 .9 J/g, indicating the ability of the polymer to crystallize from the melt at this level of modifier.

Example 4 A similar procedure as that given in Example 1 was followed except that 56 g of Avimid K polyimide powder was blended with 14 g of 1,4-bis(4-phenoxybenzoyl)-benzene lDTD) (80% Avimid K, 20 % DTD). The blend exhibited a Tg of 174C and a melt viscosity of 205 Pa.s at 385 1/g. This blend also exhiblted a bimodal Tm with endothermic maxima at 275 and 334C, dHm - 2.4, and 10.3 J/g, respectlvely. Thls result lndicates the ablllty of the polymer to crystalllze from the melt at thls modlfler level.

~xample S
A procedure slmilar to that given in Example 4 was used to prepare another 80/20 {Avimid K) / ~1,4-bis(9-phenoxybenzoyl)benzene) blend. This blend was melted and ram press spun through a spinneret (3380 micron dlameter holes, 1.14 l/d ratio, stalnless steel mesh screens ln order of distance from spinneret of 50-325-50-200-50-100-50 mesh), at 352C splnneret temperature and 1570 p9i ram pressure, and wound up at 386 to 950 meters/mln to produce tough, lustrous monofllament 19 2~61~7~

flbers which at a windup speed of 650 meters/min had the following tensile properties:
Denier c 25 - Tenacity ~g/den.) z 2.1 Elongation e 27%
Modulus (g/den.) ~ 47 Work to Break (g/den.) - 0.46 FxamDle 6 A dried blend of 80/20 (Avimid K~ / {1,4-bis(4-phenoxybenzoyl)benzene~ (DTD) was melt compounded (360C
melt temp) in a 2B mm W & P twin screw extruder to produce a uniform cylindrical strand of material which was subsequently chopped into small pellets. Melt viscosity of these pellets was found to be 280 Pa.s at 385 1/s. After drying, the pellets were fed into a Arburg 1.5 oz. injection molding machine to produce in~ection molded 1/8 in. tensile and flex bars.
Conditlons: 365C nozzle temperature, 1300 psi boost ln~ection pressure, ram speed - 5, screw speed ~ 200 rpm, mold temperature - 90C. Mechanical properties of these bars were measured and the following results were obtalned:
Tenslle modulus - 639 KPSI
Tenslle strength - 13.5 KPSI
Tenslle elongation at break - 2.7%
Flexural modulus - 636 KPSI
Flexur~l strength - 27.6 KPSI
Izod Impact - 0.~ ftlb/ln Exa~
A slmllar procedure as that glven ln Example 1 was followed except ~hat 56 g of Avlmld K polylmlde powder was blended wlth 14 g of BDTDB (~ Avlmld K, 20 %

2~187~

BDTD~). The blend exhibited a Tg of 183C and a melt viscosity of 260 Pa.s at 385 1/s. This blend also exhibited a bimodal Tm with endothermlc maxima at 272 and 329~C, total dHm ~ 9.5 J/g, indicating crystallization of the polymer from the melt at this modifier level.

~x~m~le 8 The blends prepared in Examples 1 and 2 and Comparative Example 1 were allowed to stand at room temperature for 7 days in a saturated moisture atmosphere. After blotting to remove extraneous surface moisture, each sample was immediately loaded into a TgA
cell and heated to 150C at 25~C/min and held at 150C
for 30 min. The weight loss was taken as the amount of moisture absorbed by each sample because of exposure to the humid atmosphere. The following results were obtained:

Avlmld K from Comparative Example 1:
2.0% moisture absorbed Avimid K 95% + 1,4-bis~4-phenoxybenzoyl)benzene (DTD) 5%
from Example 1:
1.6% moisture absorbed Avimid K 90% + 1,4-bis(4-phenoxybenzoyl)benzene (DTD) 10% from Example 2:
1.2% molsture absorbed ~m~2 Into a glass ~ar contalning 40 g of a commerclal poly(amlc acld) solutlon ~Du Pont Pyralln~ PI-2540), 0.295 g of 1,3-bis(4-phenoxybenzoyl)benzene (DID) were 21 2~874 - added and the ~ar was placed on a roller to dissolve the1,3-bis(4-phenoxybenzoyl~benzene (DI~) into the solution (DID ~ 5 wt % based sn total sol~ds). After dissolution, the solution was spin coated onto silicon wafers, heated to 135C for 30 minutes and then to 250C
for 1 hour to produce ~ 10 micrometer thick polyimide films. Property data for this film compared to a similarly prepared PI-2540 film containing no 1,3-bis(4-phenoxybenzoyl)benzene (DID) is included in Table 1.
Exam~le 10 A similar procedure to that given in Example 9 was followed except that the spin coated poly~amic acid) films were heated at 135C for 30 minutes and then at 300C for 1 hour to obtain the polyimide ~ilm. Property data are included in Table 1.

Exa~pl~ .ll Into a glass ~ar containing 40 g of a commercial poly(amic acid) solution (Du Pont Pyralin~ PI-2590), 0O622 g of 1,3-bis(4-phenoxybenzoyl)benzene (DID) were added and the ~ar was placed on a roller to dissol~e the 1,3-bis(4-phenoxybenzoyl)benzene (DID) into the solution ~DID - 10 wt % based on total sollds). After dissolutlon, the solution was spin coated onto silicon wafers, heated to 135C for 30 minutes and then to 250C
for 1 hour to produce - 10 micrometer thick polyimide films.
Property data for thls film compared to a similarly prepared PI-2540 film contalnlng no 1,3-bls(4-phenoxybenzoyl)benzene (DID) i5 lncluded in Table 1.

22 2~61~4 ~ E~am~le 12 A similar procedure to that glven in Example 11 was followed except that the spin coated poly~amic acl~) films were heated at 135C for 30 minutes and then at 300C for 1 hour to obtain the polyimide film. Property data are included ~n Table 1.

Examnl~ 13 Into a glass ~ar containlng 40 g of a commercial poly(amic acid) solution ~Du Pont Pyralyn~ PI-2611), 0.284 g of 1,3-bis(4-phenoxybenzoyl)benzene (DID) were added and the ~ar was placed on a roller to dissolve the 1,3-bis(4-phenoxybenzoyl)benzene (DID) into the solution (DID = 5 wt % based on total solids). After dissolution, the solution was spin coated onto silicon wafers, heated to 135C for 30 minutes and then to 250C
for 1 hour to produce ~ 10 micrometer thick polyimide films.
Property data for this film compared to a similarly prepared PI-2611 film containing no 1,3-bis(4-phenoxybenzoyl)benzene (DID) is lncluded ln Table 1.

~x~le 14 A slmilar procedure to that gi~en in Example 13 was followed except that the spin coated poly(amic acid) films were heated at 135C for 30 minutes and then at 300C for 1 hour to obtain the polyimide film. Property data ar lncluded in Table 1.

E~m~
Into a glass ~ar containing 40 g of a commerclal poly(amic acld) solutlon (Du Pont Pyralln~ PI-2611), 0.60 g of 1,3-bis(4-phenoxybenzoyl)benzene (DID) were added and the ~ar was placed on a roller to dissolve the 23 20S1~74 1,3-bis(4-phenoxybenzoyl)benzene ~DID) into the solution (DID ~ 10 wt % based on total solids). After dissolution, the solution was spin coated onto silioon wafers, heated to 135C for 30 minutes and then to 250C
for 1 hour to produce approxlmately 10 mlcrometer thick polyimide films.
Property data for this fllm compared to a similarly prepared PI-2611 film contalning no 1,3-bis~4-phenoxybenzoyl)benzene (DID) is included in Table 1.
Exam~le 16 A similar procedure to that given in Example 15 was followed except that the spin coated poly(amic acid) films were heated at 135C for 30 minutes and then at 300C for 1 hour to obtain the polyimide film. Property data are i~cluded in Table 1.

~xample 17 In a glass contalner, 95 g of an amorphous Du Pont Liquid Crystal Polymer ~LCP) of the same type as Du Pont LCP grade HX-2000 (aromatlc llquld crystalllne polyester) with an inherent viscosity of 2.0 dl/g (5 mg/ml ln 1/1 V/V 1,2-dichloroethane/p-chlorophenol) were dry blended with 5 g of oxydibenzophenone (ODBP). After drying overnight at 125C to remove any moisture present, the mixture was charged to a Haake torque rheometer (small bowl mlxer, rotor blades) at 330~C, and mlxed for 10 min at 64 rpm. Afterwards, the polymer melt was removed from the mixer via a brasQ spatula, allowed to cool to room temperature and then ground to a coarse powder in a Thomas cutter. The same procedure was followed to prepare a control sample contalning no modifler. DSC measurements ~Du Pont 1090, 20C /min, 2nd heating scan) revealed a Tg of 161C for the 2~61874 - oxydibenzophenone ~ODBP) contalning compound vs. 182C
for the control indicating a plastlcization of the Liquid Crystal Polymer (LCP) by the modifier. Gel permeation chromatography of the Liquid Crystal Polymer (LCP) samples containing the modifiers revealed essentially no degradation of the polymer molecular weight by these modifiers.

~am~le 18 In a glass container, 43.2 g of Du Pont Liquid Crystal Polymer (LCP) type HX-3000 (aromatic liquid crystalline polyester) with an inherent viscosity of 0.97 dl/g (5 mg/ml in 1/1 V/V 1,2-dichloroethane/p-chlorophenol) were dry blended with 4.8 g of 1,4-bis(4-phenoxybenzoyl)benzene (DTD) and 72 g of Harbison Walker GP7I fused silica. After drying overnight at 125C to remove any moisture present, the mixture was charged to a Haake torque rheometer (small bowl mixer, rotor blades) at 340C, and mixed for 5 mln at 64 rpm.
Afterwards, the polymer melt was removed from the mixer via a brass spatula, allowed to cool to room temperature and then ground to a coarse powder ln a Thomas cutter.
The same procedure was followed to prepare a similar compound containing only Liquid Crystal Polymer (LCP) and sllica but no 1,4-bis(4-phenoxybenzoyl)benzene (DTD) ~48 g LCP, 72 g slllca, control sample). DSC
measurements (Du Pont 1090, 20C /mln, 2nd heatlng scan) revealed a Tm of 308C for the 1,4-bis(4-phenoxybenzoyl)benzene (DTD) contalnlng compound V9.
316C for the control lndlcatlng an lnteractlon between the Llquld Crystal Polymer (LCP) and 1,4-bls(4-phenoxybenzoyl) benzene ~DTD). Slmilarly, upon cooling from the melt ln the DSC, the 1,4-bls(4-phenoxybenzoyl)benzene (DTD) contalnlng sample exhibited 2061~74 a crystallization exotherm at 232C vs. 243C for the control sample. Caplllary melt rheology (340C, L-3.1, ~ d ~ 0.029, L/d - 106.897) gave a melt viscosity of 116 - Pa.s at 100 l~s ~or the 1,4-b~s(4-phenoxybenzoyl)benzene ~DTD) containing sample vs. 130 Pa.s for the control (114 reductlon). Gel permeatlon chromatography of the L~quld Crystal Polymer (LCP) samples contain~ng the modlfiers revealed essentially no degradation of the polymer molecular welght.
Ex~ e ' 9 In a glass container 63 g of the aromatlc polyester of Bisphenol A and lsophthalic acid ~Du Pont trade name Arylon 101) was dry blended wlth 7 g of Oxydibenzophenone ~ODBP). After drying overnight at 125C to remove any molsture present, the mixture (90%
Arylon 101/10~ ODBP) was charged to a Haake torque rheometer (small bowl mlxer, high ~hear cam mixing blades) at 330C, and mlxed for 10 mln at 64 rpm.
Aftorwards, the polymer melt was removed from the mixer via a brass spatula, allowed to cool to room temperature and then ground to a coarse powder ln a Thomas cutter.
DSC measurements ~Du Pont 1090, 20C /mln, 2nd heating scan) revealed a Tg of 138C. Arylon 101 contalning no oxydibenzophenone (ODBP) but prepared under the same procesQlng condition~ was found to have a Tg of 185C
lndicating the plasticizing effect of the modifier.

A slmllar polyester (56 g) to that descrlbed in Example 13 was dry blended wlth 14 g of oxydibenzophenone (ODBP) (20 wt% ODBP). By the same procedure a8 that descrlbed ln Example 13, this blend exhlblted a Tg of 10~C vs. that of the same material 26 20~1~74 without oxydibenzophenone ~ODBP) which gave a Tg of 181C again indicating the plastlcizlng abllity of the modifier.

E~am~1~ 21 p~eparat~on of 1.4-bis~4-~ r 4-~en~yllphenoxy)henzoyl~benzene ~BDTDB~
In a 2 liter flask equipped with a nitrogen inlet, mechanical stirrer and condenser (with nitrogen outlet) were charged 100 g (0.2125 moles) of 1,4-bis(4-phenoxybenzoyl)benzene (DTD), 179 g (1.34 moles) of aluminum chloride and 800 ml of o-dichlorobenzene. To this stirring solution, 49.34 ml of benzoyl chloride (59.77 g, 0.4251 moles) in 200 ml o-dichlorobenzene were added dropwise at room temperature over 0.5 hr. The temperature rose somewhat during benzoyl chloride addition and after the addition was complete, the reaction temperature was raised to 95-100C and held for about 2.5 hrs. Hydrochloric acid generated during the reaction was swept out with nitrogen and neutralized with aqueous sodium hydroxide solution. Afterwards, the reaction solution was cooled to room temperature and precipitated into methanol. The solid product was filtered off and allowed to air dry. It was then dissolved ln hot o-dichlorobenzene, flltered through a heated coarse fritted filter, and allowed to cool and crystallize. After filtration, the white crystalline product was slurried twlce in methanol to remove residual o-dichlorobenzene and then drled under vacuum with an nltrogen bleed at 150C. A single, sharp meltlng polnt ~by DSC, 20C/min) was found for thls materlal at 287.5C ~peak maxlmum).

27 20~1~7~

~2 ~Q~aration of oxydibenzophenone (ODBP) In a similar manner to that described in the previous example, 89.96 g (0.5285 moles) of diphenyl ether and 122.7 ml (148.58 g, 1.057 moles) benzoyl chloride were dissolved in 1000 ml of o-dichlorobenzene.
In 10 - 20 gram portions, 222 g (1.665 moles) of aluminum chloride were added under stirring.
Hydrochloric acid generated during the reaction was swept out with nltrogen and neutral~zed with aqueous sodium hydroxide solution. After the complete addition of aluminum chloride, the temperature was slowly raised to 95 - 100C and the reaction was allowed to proceed at this temperature for two hours. The reaction was subsequently cooled and allowed to continue overnight at room temperature. Afterwards, the reaction was precipltated into methanol, the product was isolated by flltratlon, and then the product was recrystallized with flltering from toluene ~Melting polnt - 169 - 165C by standard melting point apparatus).

Example 23 Prep~ on of 1.3-bis(4-~he~Q~ybenzoyl)benzene ~DID) Into a 2 liter flask equipped with a mechanical stirrer, thermometer, and nitrogen inlet and outlet, were charged 210 g (1.2338 moles) of diphenyl ether, 83.9 g ~0.4132 moles) of lsophthaloyl chlorlde, and 970 ml of methylene chloride. The solution was cooled to -5C by means of and acetone ice bath and then alumlnum chloride (240 g, 1.8005 mole) was added ln six 40 g portlons. The temperature rose slightly durlng the addition of aluminum chloride and after the final addition the temperature was stabilized and held at 0C

~ 28 2061~7~

for th~rty mlnutes. The solutlon was subsequently warmed to room temperature and held there for 1 hour.
Afterwards, the solution was very slowly poured into agitated chilled demineralized water to deactivate the aluminum chloride ~maximum water temperature reached was 28C). After stirring for 10 minutes, stirr~ng was stopped and the very acidic upper layer was decanted off. The organic layer was subsequently washed several t~mes with fresh diminerallzed water to remove the acid and filtered to remove solld impurities, e.g., elemental aluminum). Afterwards, methanol was slowly added to the organic layer (about l/l on a volume basis) with stirring and the product precipitated as short, white needles. Further purification was undertaken by slurrying 3X in isopropanol followed by filtration and drying. The short needles gave a DSC melting point (20C/min) of 124C.

Example 24 preparatlon of 1.4-bi~l4-phenoxybenzoyl)benzene (DTD) A slmilar procedure to Example 23 i9 followed, except o-dlchlorobenzone i9 used as reaction solvent.
The product 19 isolated by deactivating the alumlnum chlorlde with water. The solid product is separated from o-dlchlorobenzene by filtratlon and is then washed with water and/or methanol. After drying, the product is dissolved ln hot o-dichlorobenzene, hot filtered, and allowed to recrystallize. After filtration, the product 19 washed with methanol to remove o-dichlorobenzene and then dried. Nelting point (standard meltlng point apparatùs) - 214 - 215C.

29 2~ 7~

Char,aGterization o~ Polyimide Thin Films H2O Di-ab- elec.
sorp- ~en- Const.
% Cure Ap- at slle Modu-Sam- Modl- ~emp. pear- 85% Str. % lu-~- C~E MHz, ple Polymer fler C ance RH MPa Elong. GPa ppm dry Con- P1-2611 0 250 claar 381 37 6.2 trol Ex.13 Pl-2611 5 250~lightly 341 28 6.4 cloudy Ex.15 Pl-2611 10 250cloudy 281 10 6.5 Con- P1-2611 0 300 clear 1.7 382 42 5.5 trol Ex.14 P1-2611 5 300 ~lightly 1.2 358 31 6.0 Ex.16 Pl-2611 10 300cloudy 1.0 299 13 6.5 Con- Pl-2540 0 250 clear 3.5 164 86 1.6 30 trol Ex.9 Pl-2540 5 250clear 2.8 162 72 1.9 Ex.11 Pl-2540 10 250clear 2.0 167 77 2.1 3B
Con- Pl-2540 0 300 clear 201 96 1.4 26 3.2 trol Ex.10 Pl-2540 5 300clear 2.8 158 64 1.6 Ex.12 Pl-2540 10 300clear 1.8 160 73 1.9 35 2.9

Claims (7)

1. A composition of matter comprising:
(a) a condensation polymer selected from the group consisting of polyester and polyimide, and (b) a modifier consisting essentially of a compound having a formula wherein R0 is or R1 is or R2 is or .

2. A composition of matter as defined in claim 1, wherein the modifier has a polydispersity of substantially 1.

3. A composition of matter as defined in claim 1, wherein R0 is R1 is and R2 is -H.

4. A composition of matter as defined in claim 1, wherein R0 is R1 is and R2 is -H.

5. A composition of matter as defined in claim 1, wherein R0 is R1 is and R2 is .

6. A composition of matter comprising:
(a) a condensation polymer selected from the group consisting of polyester and polyimide, and (b) a modifier consisting essentially of a compound having a formula or .

7. A composition of matter as defined in claim 6, wherein the modifier has a polydispersity of substantially 1.